Iodo­durene

Iododurene

Noudjoud Hamdouni,a* Ouarda Brihi,aMohamed Larbi Medjroubi,aJean Meinnelband Ali Boudjadaa

a

Laboratoire de Cristallographie, De´partement de Physique, Universite´ Mentouri-Constantine, 25000 Mentouri-Constantine, Algeria, andbUMR 6226 CNRS–Universite´ Rennes 1, Sciences Chimiques de Rennes, Equipe Matie`re Condense´e et Syste`mes Electroactifs, 263 Avenue du Ge´ne´ral Leclerc, F-35042 Rennes, France Correspondence e-mail: [email protected]

Received 27 October 2012; accepted 11 November 2012

Key indicators: single-crystal X-ray study;T= 293 K; mean(C–C) = 0.007 A˚; Rfactor = 0.035;wRfactor = 0.039; data-to-parameter ratio = 32.4.

The title compound (systematic name: 1-iodo-2,3,5,6-tetra-methylbenzene), C10H13I, crystallizes in the chiral space group P212121. The I atom is displaced by 0.1003 (5) A˚ from the

mean plane of the ten C atoms [maximum deviation = 0.018 (6) A˚ ]. In the crystal, there are no significant inter-molecular interactions present.

Related literature

For the crystal structure of bromodurene, see: Charbonneauet al. (1964, 1965). For the physical properties of mono-halogenated derivatives of durene, see: Balcou et al.(1965). For standard bond lengths in similar compounds, see: Allen (2002); Hopeet al.(1970).

Experimental

Crystal data

C10H13I

Mr= 260.11

Orthorhombic,P212121

a= 5.5099 (3) A˚

c= 15.1704 (6) A˚

V= 993.34 (8) A˚3

Z= 4

= 3.16 mm

T= 293 K

0.100.050.04 mm

Data collection

Nonius KappaCCD diffractometer Absorption correction: multi-scan

(SADABS; Sheldrick, 1996)

Tmin= 0.140,Tmax= 0.193

26027 measured reflections 2271 independent reflections 2036 reflections withI> 3(I)

Rint= 0.047

Refinement

R[F2_{> 2(F}2_{)] = 0.035}

wR(F2_{) = 0.039}

S= 1.04 3272 reflections 101 parameters 36 restraints

H-atom parameters constrained

max= 0.84 e A˚ 3

min= 0.71 e A˚ 3

Absolute structure: Flack (1983), 925 Friedal pairs

Flack parameter: 0.03 (4)

Data collection: COLLECT (Nonius, 2001); cell refinement:

DIRAX/LSQ(Duisenberget al., 2003); data reduction:EVALCCD

(Duisenberget al., 2003); program(s) used to solve structure:SIR2002

(Burlaet al., 2005); program(s) used to refine structure:CRYSTALS

(Betteridgeet al., 2003); molecular graphics:CAMERON(Watkinet al., 1996) andDIAMOND (Brandenburg, 2012); software used to prepare material for publication:CRYSTALS.

The authors thank the Centre de Diffractome´trie de l’Universite´ de Rennes 1 for the opportunity to collect data on the Nonius Kappa CCD X-ray diffractometer. We would also like to thank Dr Olivier Jeannin for the useful advice he provided.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2521).

References

Allen, F. H. (2002).Acta Cryst.B58, 380–388.

Balcou, Y., Gre´goire, P. & Meinnel, J. (1965).J. Chim. Phys. PCB,62, 536–538. Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J.

(2003).J. Appl. Cryst.36, 1487.

Brandenburg, K. (2012).DIAMOND. Crystal Impact GbR, Bonn, Germany. Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005).J. Appl. Cryst.38, 381–388.

Charbonneau, G., Baudour, J., Messager, J. C. & Meinnel, J. (1964).Acta Cryst. 17, 780–781.

Charbonneau, G., Baudour, J., Messager, J. C. & Meinnel, J. (1965).Bull. Soc. Fr. Mine´ral. Cristallogr.88, 147–148.

Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003).

J. Appl. Cryst.36, 220–229.

Flack, H. D. (1983).Acta Cryst.A39, 876–881.

Hope, H., Knobler, C. & McCullough, J. D. (1970).Acta Cryst.B26, 628–640. Nonius (2001).COLLECT. Nonius BV, Delft, The Netherlands.

Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996).CAMERON. Chemical

Crystallography Laboratory, Oxford, England.

Structure Reports Online

supporting information

Acta Cryst. (2012). E68, o3391 [doi:10.1107/S1600536812046557]

Iododurene

Noudjoud Hamdouni, Ouarda Brihi, Mohamed Larbi Medjroubi, Jean Meinnel and Ali

Boudjada

S1. Comment

Substituted benzene compounds are generally liquid at room temperature so relatively few crystal structure analyses of

such compounds have been reported. We have synthesized three mono-halogenated products of duren; chloro-, bromo-

and iododurene. These derivatives are solid at 293 K and their dielectric behavior depends on the nature of the

substituent, and in particular of its mass and volume. Contrary to chlorodurene the title iododurene in the solid phase has

a quite low permeability equal to only 2.6, which changes abruptly at fusion to a value of ca. 4 (Balcou et al., 1965). We

report herein on its crystal structure.

The molecular structure of the title compound is illustrated in Fig. 1. The molecule is almost planar with the I atom

displaced from the mean plane of the nine C atoms [maximum deviation 0.018 (6) Å for the methyl C atoms C7 and C9]

by 0.1003 (5) Å. The average endocyclic angles facing the I atom and the methyl groups are 124.98 (10)° and 117.41

(10)°, respectively. The structural study did not reveal any disorder and the average intramolecular bond lengths, [Car-I =

2.139 (3) Å, Car-Car = 1.400 (5) Å and Car-CMe = 1.498 (6) Å], as well as the average single Car-H bond length [0.940 Å],

agree with the distances reported in the literature [Cambridge Structural Database (Allen, 2002); Hope et al., 1970].

In the crystal, the a axis is very short, so the molecules stack along this direction (Fig. 2). The best mean plane passing

through the carbon and iodine atoms, calculated with the program Molax of CRYSTALS (Betteridge et al., 2003),

indicated that the angle between the normal to this mean plane is ca. 50.1° relative to the a axis, ca. 44.8° relative to the b

axis and ca. 74.5° relative to the c axis (Fig. 3).

The crystals obtained sublimate a little at ambient temperature. Moreover, at room temperature iododurene and the

isotypic product bromodurene (Charbonneau et al., 1964, 1965) crystallize in the same orthorhombic space group with

fixed orientations of the dipolar grouping not presenting dielectric dispersion. This fact could be interpreted by the

importance of the distribution of the masses of the substituents, that inhibit the possibility of molecular reorientation like

in chlorodurene (Balcou et al., 1965).

S2. Experimental

The title compound was synthesized by direct iodination of durene. Equimolecular quantities of iodine and durene were

dissolved in pure acetic acid at 343 K. Progressive iodination was obtained by oxidation of durene using drops of pure

sulfuric and nitric acids diluted in acetic acid. Total precipitation of iododurene was obtained by dilution with water.

Purification was done by chromatography on a silica column and finally precipitation of a solution in chloroform, giving

All H atoms were localized in a difference Fourier map. The C-bound H atoms were included in calculated positions and

treated as riding atoms: C-H = 0.94 Å for CH H atoms, and 0.95 - 0.97 Å for CH3 H atoms, with Uiso(H) = k × Ueq(C)

where k = 1.5 for CH3 H atoms and = 1.2 for other H atoms.

Figure 1

The molecular structure of the title molecule, with atom numbering. The displacement ellipsoids are drawn at the 50%

Figure 2

A view along the a axis of the crystal packing of the title compound.

Figure 3

A view along the c axis of the crystal packing of the title compound.

1-Iodo-2,3,5,6-tetramethylbenzene

Crystal data C10H13I

Mr = 260.11

Orthorhombic, P212121

a = 5.5099 (3) Å

b = 11.8839 (5) Å

c = 15.1704 (6) Å

V = 993.34 (8) Å3

Dx = 1.739 Mg m−3

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 8232 reflections

θ = 3.7–27.5°

T = 293 K

Needle, colourless 0.10 × 0.05 × 0.04 mm

Data collection Nonius KappaCCD

diffractometer

Graphite monochromator CCD scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.140, Tmax = 0.193

26027 measured reflections

2271 independent reflections 2036 reflections with I > 3σ(I)

Rint = 0.047

θmax = 27.5°, θmin = 3.7°

h = −7→7

k = −15→15

l = −19→19

Refinement

Refinement on F

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.035}

wR(F2_{) = 0.039}

S = 1.04

3272 reflections 101 parameters 36 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

W = [weight]*[1-(deltaF/6*sigmaF)2_]2

(Δ/σ)max < 0.001

Δρmax = 0.84 e Å−3

Δρmin = −0.71 e Å−3

Absolute structure: Flack (1983), 925 Friedal pairs

Absolute structure parameter: −0.03 (4)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) is used}

only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2

are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

I1 0.93848 (10) 0.80448 (4) 0.27027 (3) 0.0686 (2)

C1 0.9383 (7) 0.9098 (3) 0.1559 (2) 0.0429 (11)

C2 0.7711 (8) 0.9981 (4) 0.1533 (3) 0.0473 (16)

C3 0.7637 (8) 1.0638 (3) 0.0755 (3) 0.0483 (16)

C4 0.9270 (10) 1.0376 (4) 0.0091 (3) 0.0507 (16)

C5 1.0976 (8) 0.9513 (4) 0.0123 (2) 0.0460 (14)

C6 1.1033 (7) 0.8838 (3) 0.0887 (3) 0.0423 (14)

C7 0.5997 (12) 1.0208 (5) 0.2295 (4) 0.071 (2)

C8 0.5866 (12) 1.1574 (5) 0.0651 (4) 0.067 (2)

C9 1.2673 (11) 0.9310 (5) −0.0622 (4) 0.064 (2)

H41 0.92110 1.08070 −0.04290 0.0610*

H71 0.69240 1.03120 0.28260 0.1071*

H72 0.50940 1.08740 0.21780 0.1072*

H73 0.49160 0.95840 0.23690 0.1071*

H81 0.62710 1.21740 0.10510 0.1008*

H82 0.59650 1.18410 0.00600 0.1008*

H83 0.42310 1.13100 0.07630 0.1010*

H91 1.24630 0.98940 −0.10560 0.0971*

H92 1.43080 0.93360 −0.04010 0.0970*

H93 1.23570 0.85840 −0.08810 0.0971*

H101 1.38670 0.80080 0.14830 0.0892*

H102 1.38000 0.78630 0.04650 0.0892*

H103 1.19650 0.71900 0.10410 0.0891*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

I1 0.0831 (3) 0.0727 (3) 0.0500 (2) −0.0082 (2) −0.0036 (2) 0.0120 (2)

C1 0.046 (2) 0.044 (2) 0.0387 (19) −0.006 (2) −0.004 (2) 0.0006 (17)

C2 0.047 (3) 0.044 (2) 0.051 (3) −0.005 (2) 0.000 (2) −0.009 (2)

C3 0.046 (3) 0.040 (2) 0.059 (3) −0.004 (2) −0.011 (2) −0.007 (2)

C4 0.055 (3) 0.045 (2) 0.052 (3) −0.007 (3) −0.011 (3) 0.0031 (19)

C5 0.047 (3) 0.048 (2) 0.043 (2) −0.010 (2) −0.001 (2) −0.0036 (18)

C6 0.041 (3) 0.041 (2) 0.045 (2) −0.0034 (18) −0.0062 (18) −0.0043 (17)

C7 0.070 (4) 0.071 (3) 0.072 (4) 0.000 (3) 0.013 (4) −0.021 (3)

C8 0.063 (4) 0.052 (3) 0.087 (4) 0.008 (3) −0.019 (4) −0.005 (3)

C9 0.060 (4) 0.077 (4) 0.056 (3) −0.009 (3) 0.005 (3) −0.011 (3)

C10 0.056 (3) 0.053 (3) 0.070 (4) 0.011 (3) −0.006 (3) −0.008 (3)

Geometric parameters (Å, º)

I1—C1 2.139 (3) C7—H71 0.9600

C1—C2 1.397 (6) C7—H72 0.9500

C1—C6 1.401 (5) C7—H73 0.9600

C2—C3 1.416 (6) C8—H81 0.9600

C2—C7 1.517 (8) C8—H82 0.9500

C3—C4 1.386 (7) C8—H83 0.9700

C3—C8 1.488 (7) C9—H91 0.9600

C4—C5 1.392 (7) C9—H92 0.9600

C5—C6 1.410 (6) C9—H93 0.9600

C5—C9 1.487 (7) C10—H101 0.9700

C6—C10 1.500 (7) C10—H102 0.9500

C4—H41 0.9400 C10—H103 0.9600

I1—C1—C2 117.6 (3) H71—C7—H72 109.00

I1—C1—C6 117.5 (3) H71—C7—H73 109.00

C2—C1—C6 125.0 (3) H72—C7—H73 110.00

C3—C2—C7 121.3 (4) C3—C8—H83 110.00

C2—C3—C4 117.6 (4) H81—C8—H82 109.00

C2—C3—C8 121.3 (4) H81—C8—H83 110.00

C4—C3—C8 121.1 (4) H82—C8—H83 109.00

C3—C4—C5 125.4 (4) C5—C9—H91 109.00

C4—C5—C6 117.6 (4) C5—C9—H92 109.00

C4—C5—C9 121.2 (4) C5—C9—H93 110.00

C6—C5—C9 121.2 (4) H91—C9—H92 109.00

C1—C6—C5 117.3 (3) H91—C9—H93 110.00

C1—C6—C10 121.5 (4) H92—C9—H93 110.00

C5—C6—C10 121.2 (4) C6—C10—H101 111.00

C3—C4—H41 118.00 C6—C10—H102 109.00

C5—C4—H41 117.00 C6—C10—H103 110.00

C2—C7—H71 109.00 H101—C10—H102 108.00

C2—C7—H72 109.00 H101—C10—H103 110.00

C2—C7—H73 110.00 H102—C10—H103 109.00

I1—C1—C2—C3 −176.8 (3) C7—C2—C3—C4 179.9 (5)

I1—C1—C2—C7 1.5 (6) C7—C2—C3—C8 −0.3 (7)

C6—C1—C2—C3 2.1 (6) C2—C3—C4—C5 0.4 (7)

C6—C1—C2—C7 −179.6 (4) C8—C3—C4—C5 −179.4 (5)

I1—C1—C6—C5 178.1 (3) C3—C4—C5—C6 0.9 (7)

I1—C1—C6—C10 −3.0 (5) C3—C4—C5—C9 −179.2 (5)

C2—C1—C6—C5 −0.8 (6) C4—C5—C6—C1 −0.7 (6)

C2—C1—C6—C10 178.1 (4) C4—C5—C6—C10 −179.6 (4)

C1—C2—C3—C4 −1.8 (6) C9—C5—C6—C1 179.4 (4)